Process for preparing low boiling hydrocarbons from higher boiling hydrocarbons



. L. YOUNG ET AL 1,955,268

PARING LOW BOILING, HYDROCARBONS FROM HIGH BOILING HYDROCARBONS i F1 Dec. 11, 1930' Q 111 Ob w \ww \N QM MR C MN IhH/ILT a i a P 3 m Hm w a h N WW M QL H \w h mmw ml A Q mm ,ini..- mh 3. w u I w m a n1 1 E 0 h m d NM: u ON fi HwH h BM N llnu U0 xv m 5 .www N% April 17, 1934. p

. PROCESS FOR PRE Patented Apr. 17, 1934 UNITED STATES PATENT OFFICE;

HYDROCARBONS Philip Li Young and Durand Churchill, .m, New York, N. Y., assignors to Standard-I. G. 00.

Application December 11, 1930, Serial No. 501,548

Claims.

This invention relates to the production of lower boiling hydrocarbons from higher boiling hydrocarbons and more specifically comprises a combination of cracking and hydrocycliformation 5 in which the heaviest fraction of the product from each stage is continuously returned to the cracking step. 1

Our process will be fully understood from the following description and the drawing which is a semi-diagrammatic view in sectional elevation of a suitable type of apparatus for accomplishing our process and indicates the flow of the various materials. y

In the drawing the letter A designates a cracking unit and the letter B a hydrocycliformation unit. Reference character 1 designates a feed pump which draws fresh oil from any suitable source (not shown) and forces-it through coil 2 and lines 3 and 341 into heating coil 4 mounted in a suitable furnace setting 5 which may be fired by gas or other suitable means. The hot oil flows through line 6 into cracking chamber 7 fromwhich cracked products leave through line 8, flow past pressure reduction valve8a and discharge into drum 9 wherein tar settles out and may be drawn off through line 10. The remaining I cracked products in vapor form flow through line 11 into fractionating tower 12 equipped with cooling coil 2, pan 13 and heating coil 14.

Uncondensed vapors flow out of tower 12 through line 15 into cooler 16 and discharge thence into drum 17 fitted with gas release line 18 and liquid draw-off line 19. The heaviest fraction of the condensate collects at the bottom of the tower 12 and is drawn off through line 20 and discharged into drum 21 fitted with gas release line 22 and liquid draw-oil line 23. This fraction may be drawn through line 24 by pump 25 and forced through lines 26, 2'7 and 3a into heating coil 4 and thence returned to cracking chamber '7.

I The lighter fractions of the condensate in tower 12 collect on pan 13 and flow through line 28 into drum 29 fitted with gas release line 30 and liquid draw-off line 31; This fraction may bewithdrawn from drum 29 through line 32 by pump 33 and forced through line 34 to the hydrocycliformation unit 13.

The cracked products fromdrum 29 fiow through line 34 into heating coil 35 mounted in suitable furnace setting 36 fired by gas or other means and the hot oil flows thence through line 37 and discharges through a suitable series of openings into high pressure reactor 38, which is adapted to withstand high temperatures and they are partially cooled by interchange of heat with fresh feed oil, and discharge through line 43 into separating drum 44 from which liquid products flow through line 45 past pressure reduction valve 45a, and enter fractionating tower 46, which is equipped with cooling coil 4'? and heating coil 48.

Uncondensed vapors leave tower 46'through line 49 pass through cooler 50 and the condensate is collected in drum 51 equipped with'gas release line 52 and liquid draw-off line 53 through which the product may be withdrawn and sent to storage or to equipment (not shown) for further treatment. The heavier fraction of the condensate in tower 46 may be withdrawn through line 54 and collected in drum 55 fitted with gas release line 56 and liquid draw-off line 5'7. This fraction may be drawn through line 58 by pump 89 59 and returned through lines 60, 27, 3a, coil 4 and line 6 to cracking chamber '7. Lighter fractionsof the condensate in tower 46 collect on pan 61 from which they flow through line 62 into drum 63 fitted with gas release line 64 and liquid 8 draw-off line 65, from which they may be withdrawn through line 66 by pump 67 and forced through line 68 to line 34 and thence returned through coil 35 to reactor 38.

Fresh hydrocarbon oil of substantially the same 9 boiling range and characteristics as the intermediate fraction of the cracked product sent to the hydrocycliformation unit may be drawn from suitable storage (not shown) through line 69 and forced by pump 70 through coil 47, line 71 and heat exchanger 42 and passed thence through line '72 which meets line 34 carrying hot intermediate cracked product and thus passed through coil 35 into reactor 38.

Hydrogen or a gas rich in free hydrogen is drawn from a suitable holder (not shown) through line '73 into compressor 74 in which it is compressed to a high pressure, substantially that maintained in reactor 38, and is forced through line '75 which meets oil line 34, so that the oil may be mixed with hydrogen before passing through the coil. Hydrogen may also be admitted directly to the reactor through line 76.

The uncondensed gases in the separating drum 44 contain a substantial quantity of free hydrogen which may be advantageously recirculated to 'the reactor. These gases leave separating drum 44 through line 7'7, and may pass first through a cooler 78 in which light hydrocarbons may be condensed. The light condensate and remaining gases pass through line 79 into separating drum 80, from which the liquid flows through line 81 to line 45, and the gas flows through line 82 into purification system 83 in which hydrogen sulfide, ammonia and other impurities as well as uncondensed hydrocarbons are removed, for example by scrubbing with oil, alkali or water or any combinations of these, and the purified gas flows thence through line 84 to booster compressor 85 which recompresses it to reactor pressure and returns it through line 86 to fresh hydrogen line Catalytic materials that may be used in'reactor 38 comprise the oxides or sulfides of metals of the II, IV and VI groups of the periodic system or mixtures of these. The catalytic material may be in the form of lumps of convenient shape and size which may be supported on trays or by other means in the reactor. The oxides or sulfides of molybdenum, chromium and tungsten preferably incombination with the oxides of zinc or magnesium may be mentioned as suitable catalytic materials and all of these are characterized by immunity to sulfur poisoning.

In the operation of my process any high boilinghydrocarbon oil may be used as fresh feed stock to the cracking unit A for example, heavy naphthas, gas oils, reduced crudes and other heavy fractions. The fresh feed is heated in coil 4 to a temperature above about 750 F. and preferably between about 800 and-900 F. Cracking chamber 7 may be maintained at temperatures above about 725 F. and under normal or superatmospheric pressure. In the latter case, the pressure is preferably in excess of 500 pounds per square inch. Pressures of 750 or 1000 pounds per square inch or higher and temperatures of 800 F. to 900 F. are especially satisfactory. It will be understood, however, that cracking unit A may be of any preferred type and that the conditions of operation may be varied within wide limits.- When operating under superatmospheric pressure the reduction in pressure on the cracked products at valve 8a will generally cause the major quantity of the oil to vaporize when discharged into drum 9. The pressure prevailing in drum 9 may be atmospheric, but is preferably higher, say 25 to 100 pounds per square inch,'or higher. The cracked vapors from which tar has been removed are separated in tower 12 into three fractions having approximately the following characteristics:

The light distillate is especially suitable for motor fuel and may bebl'ended with the light distillate produced in the hydrocycliformation unit 3 which is collected in drum 51. It may be subjected to the usual acid, clay or other finishing treatment as will be understood.

The intermediate fraction is subjected to hydrocycliformation in unit B. The term hydrocycliformation is used to define a process for the production of anti-detonating motor fuels by destructive hydrogenation of hydrocarbon oils. It leaves tower 12 at a temperature above about 400 F. and may be advantageously mixed at this point with fresh hydrocarbon oil of approximately the same boiling range and characteristics which has been preheated to about the same temperature in heat interchanger 42. The cracked oil or mixture of cracked and fresh oil may then be forced by pump 33 under pressure in excess of 20 atmospheres, preferably 100 or 200 atmospheres or higher into coil 35 in which it is heated to a temperature in excess of 850 F., preferably between about 900 and 1000 F. and thence discharged into reactor 38. The oil is preferably admixed with hydrogen before passage through the coil. Reactor 38 is maintained at temperatures between about 900 and 1100 F. principally by the heat evolved in the hydrogenation of the oil and by the heat introduced with the oil, but it will be understood that additional heat may be furnished by other means such as by electrical heaters (not shown) placed inside the reactor. The pressure in the reactor is also in excess of 20 atmospheres and preferably 100 or 200 atmospheres or higher.

The hot products which leave the reactor are only partially cooled in heat exchanger 42 so that the liquid collected in drum 44 is at a temperature substantially above 400 F. and therefore on the reduction of pressure at valve 45a to substantially atmospheric pressure it is almost completely vaporized before discharging into the 'fractionating tower 46. However, it will be understood that the liquid may be more completely cooled, for example, by a cooler inserted in line 45, before it is discharged into tower 46. Hydrocarbons remaining uncondensed at the temperature in drum 44 may be cooled in cooler 78 and this condensate may be combined with the liquid in drum 44. The hydrocycliformed product is likewise separated into three fractions having approximately the following characteristics:

Light distillate Gravity A.'P.I. 50 to 60 Initial boiling pt 90 to 100 F. Final boiling pt 350 to 450 F.

. Intermediate fraction Gravity A. RI 20 to 30 Initial boiling pt 350 to 450 F. Final boiling pt. 550 to 725 F.

' Heavy fraction Gravity a 10 to 20 Initial boiling pt Above 550 F.

The initial and flnal boiling points given here and above refer to operation with good fractionation. Where, however, fractionation is poor, it

should be understood that the initial boiling point is the temperature at which about 3.5 to 7% distills over, and the final boiling point the temperature at which about 90 to 97% distills over.

The yields of each fraction obtained will depend very largely on the nature and boiling range of the oil being treated and on the conditions of treating. The yield of distillate may vary from 50 to 80% by volume on the fresh feed charged to the hydrogenation zone, and the yields of intermediate frac- 15o tion and heavy fraction expressed as volume on operation of both steps may be varied within wide freshfeed may vary from 10 to 20% or more and limits. Our invention is limited only by the folfrom 5 to 10% or more respectively. lowing claims in which we wish to claim all nov- The light distillate has marked anti-detonation 'elty inherent in it. qualities, having a knock rating equivalent to that We claim: I of normal heptane containing or more of iso- 1. Improvedprocess for preparing lower boiling octane. It is "also characterized by very low sulfur hydrocarbons from higher. boiling hydrocarbons, content, generally below about .015, and is stable which comprises cracking said higher boiling in" respect to color and gum formation. As menhydrocarbons, separating the cracked product tioned above this light distillate may be advaninto a light fraction suitable for motor fuel, an tageously blended with the light distillate obintermediate distillate fraction, aheavy distillate tained in the cracking step. The intermediate fraction and aresiduum, subjecting the intermefraction is preferably recycled to reactor 38 for diate distillatefraction to hydrocycliformation, further hydrocycliformation. separating the hydrocycliformation product into The heavy fractions from both the cracking a light fraction suitable for motor fuel, an interstep and the hydrocycliformation step are prefermediate actio d a h y fraction, and p ably returned to the cracking operatioh. The tar t heavy distillate fra i n of t e cracked from the cracking coil may also be returned to Dmduct the heavy residual fraction of the the cracking operation, and this is advantageous hydrocycliform d Product to t craiiking Z0118- when the maximum yield of gasoline is desired P S according to l im 1 in which the d fuel 011 is t, nt d, cracking step is carried out at a temperature It has been found that higher boiling fractions, above -fl under Pressure in ce s of 500 say those with initial boiling point above about P0111165 P q e inch, and the hydrocyclifor- 625 F, have a, great tendency t ok in th hymation step is carried out at a temperature bea for suitable hydrocycliformation of the lower boilbe used. The ratio of partial pressure of oil to cultly vaporizable tarry fraction, subjecting an drogenation zone unless partial pressures of hytween about 900 and 1100 F. and under pressure drogen considerably in excess of those required in EXCESS 0f 0 a p es.

3. Process according to claim 1 in which the ing fractions are used. "It is, therefore,desirable lig t d t at Suitable for motor fu Separated to return these high boiling fractions for further from the P odu t Of ac Zone are ble ded. cracking. 4. Improved process for preparing lower boiling 106 The quantity of hydrogen used varies greatly hydrocarbons-from higher boiling hydrocarbons, I with the nature of the particular oil being treated. which comprises cracking the higher boiling hy- In general 2000, 3000 or 5000 cubic feet of hydrodrocarbons, separately removing from the cracked. gen per barrel of oil is suificient, but more may product a gasoline, fraction and a heavy difii- 110 hydrogen is roughly about 1: 3, when operating intermediate distillate fraction of the cracked at 200 atmospheres total pressure. The partial product boiling within the temperature range of pressure of oil may vary from20 to 70 atmos- 350 and 725 F. to hydrocycliformation, removing pheres and the partial pressure of hydrogen and a gasoline fraction from the product of hydrocyother gases from about 130 to 180 atmospheres. cliformation, separating from the remaining The space velocity in the hydrogenation zone is product of hydrocycliformationa fraction boilpreferably from 1.0 to 3.0 volumes of oil per v'oling between the limits of 350 and 550 F., returnume of reaction space per hour, although higher ing this fraction to the hydroeyclif'ormation step 3 or lower space velocities may. be used. I l and passing the residue of the hydrocyclifiorma- The present process is-particularly applicable tionproduct to the cracking step. to those types of oil, for example highly aromatic 5. Improved process for preparing lower boiling stocks, which upon hydrocycliformation produce hydrocarbons suitable for motor fuel from higher considerable quantities of very high boiling and boiling hydrocarbon oils, which comprises crackrefractory compounds. By this process these reing said higher'boiling hydrocarbon oils, separatfractory products can be immediately withdrawn ing the cracked product into .a gasoline fraction, 1

w from the hydrocycliformation unit and subjected an intermediate fraction boiling within the apto further cracking before resubmitting them to proximate temperature range of 350 and 625 F., hydrccycliformation. The efiect of this is to a heavy relatively higher boiling distillate frackeep the hydrocycliformation zone practically tion and a residuum, subjecting said intermediate entirely free from fractions other than those fraction to hydrocycliformation, separating the most easily hydrocycliformed and in this way to products thereof into a gasoline fraction, an ingreatly prolong the active life of the catalyst and 'termediate fraction of about the same boiling to enableeflicient operation for a longer period; 7 range as the intermediate fraction obtained from a This invention is not limited by any theory of the product of cracking, and a heavy residue, the mechanism of the reactiona nor by'any parreturning the intermediate fraction of the hydroticular methods of cracking and hydrogenation 'cycliformed product to the hydrocycliformation' which have been described for purposes of illusprocess-and passing the heavy residue of the tration'only. The cracking may either be in 1iq-'- hydrocycliformed productto thecracking process.

c with a coil alone-or with a coil andsoaking uid phase orvapor'phase and may be'conducted v PHILIP L. .YOUNG. 1

DURAND CHURCHILL, JR.

It alsobel'l'lnderstood that the methods of 

